Release agent, resin composition and molding

Abstract

To provide a release agent which has heat resistance at least equivalent to that of a coal-based wax such as a montan wax, and is excellent in mold releasability, and a resin composition.SOLUTION: A release agent contains a compound (I) obtained by reaction of a carboxy group of a composition (A) which contains 75 to 100 mass% of a compound (A') having 0 to 25 mass% of polyethylene and a saturated hydrocarbon chain having 24 or more average carbon numbers, having the one carboxy group, and having polydispersity Mz / Mn of 1.8 or less, and has polydispersity Mz / Mn of 1.8 or less, and a hydroxy group of a composition (B) which contains 75 to 100 mass% of a compound (B') having 0 to 25 mass% of polyethylene and a saturated hydrocarbon chain having 24 or more average carbon numbers, and having the one hydroxy group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a mold release agent, a resin composition, and a molded article. [Background technology]

[0002] Improving the productivity and quality of molded articles requires excellent mold releasability. One method for improving mold releasability is to use a mold release agent (wax). Patent Document 1 discloses an additive for thermoplastic resin processing, which is obtained by a condensation reaction between a linear saturated monocarboxylic acid having 14 to 30 carbon atoms and a linear saturated monohydric alcohol having 14 to 30 carbon atoms or a dihydric to hexahydric polyhydric alcohol having 2 to 30 carbon atoms, and which comprises an ester compound having an acid value of 3 mg KOH / g or less and a hydroxyl value of 5 mg KOH / g or less. Patent Document 2 discloses a resin composition containing a copolymer A having a styrene-based monomer unit and a vinyl cyanide-based monomer, and at least one mold release agent B selected from aliphatic alcohols and fatty acids having 16 or more carbon atoms. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-059744 [Patent Document 2] International Publication No. 2022 / 065222 Summary of the Invention [Problem to be solved by the invention]

[0004] Traditionally, natural waxes such as coal-based waxes like montan wax have been used. However, the production volume of coal-based waxes has been decreasing due to the recent trend toward decarbonization. Furthermore, natural waxes have the problem of unstable quality.

[0005] The present disclosure has been made in view of the above background, and an object of the present disclosure is to provide a release agent having heat resistance equal to or greater than that of conventional coal-based waxes such as montan wax and having excellent mold releasability, as well as a resin composition containing the release agent. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that the problems of the present disclosure can be solved in the following aspects, and have thus completed the present disclosure. [1]: an ester compound (I) represented by (A')-(B') (hereinafter referred to as compound (I)) obtained by reacting a carboxy group of a composition (A) (hereinafter referred to as composition (A)), which contains 0 to 25 mass% of polyethylene and 75 to 100 mass% of a saturated hydrocarbon-based compound having a saturated hydrocarbon chain with an average carbon number of 24 or more, one carboxy group, and a polydispersity index Mz / Mn of 1.8 or less (hereinafter referred to as compound (A')), with a hydroxy group of a composition (B) (hereinafter referred to as composition (B)), which contains 0 to 25 mass% of polyethylene and 75 to 100 mass% of a saturated hydrocarbon-based compound having a saturated hydrocarbon chain with an average carbon number of 24 or more and one hydroxy group (hereinafter referred to as compound (B')); Compound (II) represented by (A')-(C)-(A') obtained by reacting the carboxy group of compound (A') with the reactive functional group of linking group (C), and a mixture (III) for obtaining compound (I), the mixture containing composition (A) and composition (B) containing a precursor of compound (I); A release agent comprising at least one selected from the group consisting of: [2]: The release agent according to [1], wherein the linking group (C) is represented by general formula (1). [ka] (wherein X represents a divalent group selected from the group consisting of an optionally substituted linear or branched hydrocarbon group, an optionally substituted alicyclic hydrocarbon group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, a metal atom, and a group represented by general formula (2), or a divalent group formed by combining two or more of the same or different groups selected from the above group; Y 1 , Y 2 represent, independently of one another, a hydroxy group, a thiol group, an amino group, or an isocyanate group. [ka] (However, Z 1 , Z 2 are each independently -O-, -S-, -SO2-, -Si(Me)2-, -N=N-, -NH-, and -NR 4 - is a divalent group selected from the group consisting of R 1 ~R 3 each independently represents a divalent group selected from the group consisting of a linear or branched hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, and -C(CF3)2-, or a divalent group formed by combining two or more of the same or different groups selected from the above group; R 4 is a linear or branched hydrocarbon group having 1 to 12 carbon atoms, and n is an integer of 0 or more. [3]: The release agent according to [2], wherein the metal atom of X is selected from the group consisting of Ca, Mg, and Zn. [4]: The release agent according to any one of [1] to [3], which contains the compound (I) or (II) and further contains the composition (A). [5]: The release agent according to any one of [1] to [4], further comprising a polyethylene component. [6]: the dipole moments S of compounds (I) and (II) calculated by quantum chemical calculation are 1.7≦S≦4.7 Debye; The release agent according to any one of [1] to [5], wherein in the case of the mixture (III), the dipole moment S of the compound (I) obtained from the mixture (III) is 1.7≦S≦4.7 Debye. [7]: A resin (G) and the release agent according to any one of [1] to [6], A resin composition comprising the release agent in an amount of 0.01 to 20 parts by mass per 100 parts by mass of resin (G). [8]: A molded article formed from the resin composition according to [7]. [Effects of the Invention]

[0007] The present disclosure has the excellent effect of providing a release agent having heat resistance equal to or greater than that of conventional coal-based waxes such as montan wax and excellent mold releasability, as well as a resin composition containing the release agent. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram showing a 1H-NMR chart of the compound according to Synthesis Example 3. [Figure 2] FIG. 1 is a diagram showing an IR spectrum of a compound according to Synthesis Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure will be described in detail below. It goes without saying that other embodiments are also included within the scope of the present disclosure as long as they are consistent with the spirit of the present disclosure. In this specification, a numerical range specified using "to" includes the lower and upper limits of the numerical values ​​written before and after "to". Unless otherwise noted, the various components appearing in this specification may be used independently, either singly or in combination of two or more types. The numerical values ​​described in this specification refer to values ​​obtained by the methods described in the Examples below.

[0010] 1. Release agent The release agent of the present disclosure (hereinafter also referred to as the present release agent) contains at least one of the following compounds (I), (II), and mixture (III). Compounds (I) and (II) each independently represent one or more compounds. Similarly, compound (A') contained in composition (A) and compound (B') contained in composition (B) in mixture (III) each independently represent one or more compounds. It is preferable that one of compounds (I), (II), and mixture (III) is used as the main component of the present release agent. The term "main component" refers to the component with the largest amount (parts by mass) in the release agent (solid content). When one or more compounds are contained in each of compounds (I), (II), and mixture (III), the total amount (parts by mass) of the main component is compared. Mixture (III) is determined based on the total amount of composition (A) and composition (B).

[0011] Compound (I): An ester compound represented by (A')-(B') obtained by reacting the carboxy groups of a composition (A) (hereinafter referred to as composition (A)), which contains 0 to 25 mass% of polyethylene and 75 to 100 mass% of a saturated hydrocarbon-based compound having a saturated hydrocarbon chain with an average carbon number of 24 or more and one carboxy group (hereinafter referred to as compound (A')), and which has a polydispersity index Mz / Mn of 1.8 or less, with the hydroxy groups of a composition (B) (hereinafter referred to as composition (B)), which contains 0 to 25 mass% of polyethylene and 75 to 100 mass% of a saturated hydrocarbon-based compound having a saturated hydrocarbon chain with an average carbon number of 24 or more and one hydroxy group (hereinafter referred to as compound (B')). Compound (II): A compound represented by (A')-(C)-(A') obtained by reacting the carboxy group of compound (A') with the reactive functional group of linking group (C). Mixture (III): A mixture for obtaining compound (I), comprising composition (A) containing a precursor of compound (I) and composition (B).

[0012] The polydispersity of composition (A) means the ratio (Mz / Mn) of the z-average molecular weight (Mz) of the compound to the number-average molecular weight (Mn) of the compound.

[0013] The saturated hydrocarbon chain means an alkyl group or an alkylene group, and the alkyl group and the alkylene group are linear hydrocarbon chains.

[0014] The proportion of at least one of compounds (I), (II), and mixture (III) in the release agent (solid content) (the total proportion when more than one is contained) is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 70% by mass or more. By using a release agent with the proportion of 40% by mass or more, the fluidity, releasability, and continuous releasability of the resin composition described below are improved. This release agent may be a mixture of any combination selected from compounds (I), (II), and mixture (III).

[0015] From the viewpoint of flowability, a release agent containing either compound (I) or (II) as a main component and further containing composition (A) is preferred. From the viewpoint of flowability of the resin composition, the content of composition (A) is preferably 1 to 50 mass%, more preferably 5 to 20 mass%, of 100 mass% of the release agent.

[0016] From the viewpoint of improving compatibility with the resin composition, the release agent preferably contains a polyethylene component. From the viewpoint of improving compatibility with the resin composition, the polyethylene component is preferably 5 to 25 mass %, more preferably 15 to 20 mass %, of 100 mass % of the release agent.

[0017] The release agent may contain components other than those described above within the scope of the present disclosure. For example, it may contain unreacted raw materials. It may also contain a mono-substituted compound of compound (II). Furthermore, compound (II) may contain a mono-substituted compound represented by (A')-(C) in addition to compound (II) represented by (A')-(C)-(A').

[0018] In the present release agent, the dipole moment S of the main component (however, in the case of mixture (III), the dipole moment S of compound (I)) calculated by quantum chemical calculation is preferably 1.7≦S≦4.7 Debye.

[0019] By using the compound (I) or (II) having a dipole moment S within the above range as the main component, the release properties can be more effectively improved. When the present release agent is used as an external lubricant, it is desirable that the compatibility between the release agent and the resin is low. On the other hand, when the present release agent is used as an internal lubricant, it is desirable that the compatibility between the release agent and the resin is high. According to the release agent of the present disclosure, by using the compound (I) or (II) having at least two saturated hydrocarbon chain structures with an average carbon number of 24 or more and by setting the dipole moment S (however, in the case of the mixture (III), the dipole moment S of the compound (I)) to 1.7≦S≦4.7 Debye, it is possible to achieve both external and internal lubricant properties. The lower limit of the dipole moment S is more preferably 1.9 Debye, and even more preferably 2.1 Debye. The upper limit of the dipole moment S is more preferably 4.5 Debye, and even more preferably 4.3 Debye.

[0020] The dipole moments S of compounds (I) and (II) are values ​​calculated by quantum chemical calculations according to the following procedure: The three-dimensional structures of compounds (I) and (II) are modeled using the software GaussView6 based on the following rules. (1) The saturated hydrocarbon chains of each of the compounds (A') and (B') have a linear structure. (2) Calculate the dipole moment S of the conformation of compound (II) in which the saturated hydrocarbon chains of compound (A') face the same direction with the linking group (C) as the axis (the two saturated hydrocarbon chains of (1) approach each other with the linking group (C) as the axis). (3) Bond angles and bond lengths are not changed. The bond angles here refer to the default angles between three atoms when molecular modeling is performed with GaussView6, and the bond lengths refer to the default distances between two atoms when molecular modeling is performed with GaussView6. The structure after adjusting the drawn three-dimensional structure using the clean function of GaussView6 was used as the initial structure for calculations. (4) Salt compounds consisting of ionic bonds are composed of corresponding cations and anions. However, the input file for the Gaussian16 software does not correspond to a system in which cations and anions coexist. Therefore, the salt compounds in the examples and comparative examples in this specification were calculated as cations. The calculation method using Gaussian16 software was DFT, the density functional was B3LYP, and the basis set was 6-31G(d), and a structural optimization calculation of the input initial structure was performed. The obtained optimized structure was loaded into GaussView6 software, and the calculated dipole moment S was confirmed.

[0021] The dipole moment S of the mixture (III) is determined by the dipole moment of the compound (I) obtained from the compound (A') and the compound (B'). When the mixture contains multiple types of the compound (A') and / or the compound (B'), the dipole moment S of the compound (I) obtained from each combination is calculated, and the dipole moment S of the entire compound (I) is calculated by multiplying the ratio of each compound (I) obtained.

[0022] When there are two or more main compounds (I), the content is determined as follows. Dipole moment of compound (I) = Dipole moment of compound (I) 1 × blending ratio + Dipole moment of compound (I) 2 × blending ratio + Compound (I) n x blending ratio (n is an integer of 1 or more). The same applies when the main compound is compound (II).

[0023] The release agent of the present disclosure has a resin-compatible portion and an incompatible portion, thereby providing a release agent with excellent mold releasability. The reason for this is believed to be that the release agent contains compound (I) or (II), or mixture (III) for obtaining compound (I), derived from composition (A) having a saturated hydrocarbon chain with an average carbon number of 24 or more and a polydispersity index Mz / Mn of 1.8 or less. This ensures compatibility between the resin and the release agent in the surface layer, preventing bleed-out and appropriately suppressing compatibility with the resin.

[0024] When used as an internal lubricant, it is preferable that the release agent has high compatibility with the resin. According to the release agent of the present disclosure, by using the compound (I) or (II) derived from the composition (A) having a saturated hydrocarbon chain with an average carbon number of 24 or more and a polydispersity index Mz / Mn of 1.8 or less, or the mixture (III) for obtaining the compound (I), it is possible to maintain low compatibility between the resin and the release agent while ensuring compatibility between the resin and the release agent. Therefore, the release agent is particularly suitable for applications where both external and internal lubricant properties are required, particularly in the case of thin or small molded articles. In the case of large molded articles, the release agent is particularly suitable for use as an external lubricant, where excellent compatibility is achieved in the surface layer, preventing bleed-out and realizing mold releasability.

[0025] 1-1. Composition (A) Composition (A) contains 0 to 25 mass% polyethylene and 75 to 100 mass% saturated hydrocarbon-based compound (compound (A')) having a saturated hydrocarbon chain with an average carbon number of 24 or more, one carboxy group, and a polydispersity index Mz / Mn of 1.8 or less. Composition (A) may consist solely of compound (A'). While this is not strictly a composition, it is referred to as composition (A) for convenience. Composition (A) may contain components other than polyethylene and compound (A') without departing from the spirit of the present disclosure. The total amount of polyethylene and compound (A') relative to 100 mass% of composition (A) is preferably 75 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, or even substantially 100 mass%. Examples of other components that may be contained in composition (A) include hydrocarbon compounds having partially unsaturated bonds. The carboxyl group is not only a -COOH group, but also a cation other than hydrogen ion and -COO - From the viewpoint of high chemical resistance and low solubility, a long-chain linear primary carboxylic acid is preferred.

[0026] The lower limit of the average number of carbon atoms in the saturated hydrocarbon chain of compound (A') is more preferably 30, even more preferably 38, and particularly preferably 50. The upper limit of the average number of carbon atoms in the saturated hydrocarbon chain of compound (A') is preferably 100, more preferably 90, even more preferably 80, and particularly preferably 72. By setting the lower limit of the average number of carbon atoms in the saturated hydrocarbon chain of compound (A') to 24 or more, the vapor pressure can be lowered, and volatility during molding processing can be significantly suppressed. In addition, the lubricity effect can be effectively exerted.

[0027] A suitable example of the compound (A') is a polymer represented by the following general formula (3). [ka] Here, n2 is an integer of 11 or more. By using such a polymer, an inexpensive release agent can be provided. For example, the polymer can be produced by polymerizing ethylene and introducing a carboxyl group to the terminal. Alternatively, a carboxyl group-containing compound can be synthesized from polyethylene. The upper limit of n2 is not particularly limited, but is preferably 49, more preferably 44, and even more preferably 39, from the viewpoint of fluidity. The lower limit of n2 is preferably 14, more preferably 17, from the viewpoint of heat resistance.

[0028] The Mn (number average molecular weight) of the composition (A) is preferably from 500 to 5,000, more preferably from 600 to 4,000, and even more preferably from 700 to 3,000, from the viewpoint of flowability. By using a release agent containing compound (I), (II), or mixture (III) obtained using composition (A) having a polydispersity Mz / Mn of 1.8 or less and compound (A') having a polydispersity Mz / Mn of 1.8 or less, the resin composition has excellent sharp melt properties. Furthermore, an increase in viscosity of the resin composition can be suppressed. The polydispersity Mz / Mn of composition (A) is more preferably 1.78 or less, and even more preferably 1.75 or less. The lower limit of the polydispersity Mz / Mn is 1. Similarly, the polydispersity Mz / Mn of compound (A') is more preferably 1.78 or less, and even more preferably 1.75 or less. Composition (A) having a polydispersity Mz / Mn of 1.8 or less is commercially available. The polydispersity Mz / Mn may also be adjusted by adding compound (A') or polyethylene.

[0029] 1-2. Composition (B) Composition (B) contains 0 to 25% by mass of polyethylene and 75 to 100% by mass of a saturated hydrocarbon compound (compound (B')) having a saturated hydrocarbon chain with an average carbon number of 24 or more and one hydroxy group. Composition (B) may consist solely of compound (B'). In this case, although it is not strictly a composition, it is referred to as composition (B) for convenience. Composition (B) may contain components other than polyethylene and compound (B') within the scope of the present disclosure. The total of polyethylene and compound (B') is preferably 75% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass, and may even be substantially 100% by mass, relative to 100% by mass of composition (B). Composition (B) may have any structure (e.g., a partially unsaturated bond or a reactive substituent) within the scope of the present disclosure. From the viewpoint of improving mold releasability and heat resistance, a long-chain linear primary alcohol is preferred.

[0030] The lower limit of the average number of carbon atoms in the saturated hydrocarbon chain of compound (B') is more preferably 30, even more preferably 42, and particularly preferably 50. The upper limit of the average number of carbon atoms in the saturated hydrocarbon chain of compound (B') is preferably 100, more preferably 90, even more preferably 80, and particularly preferably 72.

[0031] A suitable example of the compound (B') is a polymer represented by the following general formula (4). [ka] Here, n4 is an integer of 11 or more. By using such a polymer, a mold release agent can be provided at low cost. For example, the polymer can be prepared by polymerizing ethylene and introducing a hydroxyl group to the terminal. The upper limit of n4 is not particularly limited, but from the viewpoint of fluidity, it is preferably 49, more preferably 44, and even more preferably 39. The lower limit of n4 is preferably 14, more preferably 17, from the viewpoint of heat resistance.

[0032] The Mn (number average molecular weight) of the composition (B) is preferably from 500 to 5,000, more preferably from 600 to 4,000, and even more preferably from 700 to 3,000, from the viewpoint of flowability.

[0033] 1-3. Linking group (C) The linking group (C) serves to link two molecules of the compound (A'). The linking group (C) is a compound having two or more reactive functional groups capable of reacting with the carboxyl group of the compound (A'). The number of reactive functional groups is preferably two. The two reactive functional groups may be the same or different, but are preferably the same. A preferred example is the following general formula (1). [ka] X represents a divalent group selected from the group consisting of an optionally substituted linear or branched hydrocarbon group, an optionally substituted alicyclic hydrocarbon group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, a metal atom, and a group represented by general formula (2), or a divalent group formed by combining two or more of the same or different groups selected from the above group. 1 , Y 2 represent, independently of one another, a hydroxy group, a thiol group, an amino group, or an isocyanate group. [ka] Z 1 , Z 2 are each independently -O-, -S-, -SO2-, -Si(Me)2-, -N=N-, -NH-, and -NR 4 - is a divalent group selected from the group consisting of R 1 ~R 3 each independently represents a divalent group selected from the group consisting of a linear or branched hydrocarbon group having 1 to 12 carbon atoms, which may have a substituent; an aromatic hydrocarbon group having 6 to 12 carbon atoms, which may have a substituent; and -C(CF3)2-; or a divalent group formed by combining two or more of the same or different groups selected from the above group, and n represents an integer of 0 or greater. There is no upper limit for n, but it is preferably 100, more preferably 50, and even more preferably 10. Y 1 , Y 2 may be the same or different, but are preferably the same. 4 Examples of the alkyl group include linear or branched hydrocarbon groups having 1 to 12 carbon atoms. Suitable examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

[0034] Suitable examples of X include linear or branched hydrocarbon groups such as methylene, ethylene, propylene, trimethylene, methylethylene, tetramethylene, 1-methyltrimethylene, 2-methyltrimethylene, pentamethylene, 1-methyltetramethylene, 2-methyltetramethylene, hexamethylene, 1-methylpentylene, 2-methylpentylene, 3-methylpentylene, 1-ethyltetramethylene, 2-ethyltetramethylene, heptamethylene, and octamethylene; Alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, and cycloheptyl groups; aromatic hydrocarbon groups such as phenylene, tolylene, xylylene, and naphthylene groups; Examples include metal atoms such as Ca, Mg, Zn, etc. The structure represented by general formula (2) is also suitable.

[0035] R1 ~R 3 Suitable examples of each independently include the linear or branched hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups exemplified above for X.

[0036] Specific examples of the linking group (C) include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin, and diethanolamine; alicyclic diols such as cyclohexanediol, cyclohexanedimethanol, and hydrogenated bisphenol A; and aromatic diols such as an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A. Further examples include aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, and hydrogenated xylylene diisocyanate; and aromatic diisocyanates such as diphenylmethane diisocyanate, xylylene diisocyanate, dimethyldiphenylene diisocyanate, and tolylene diisocyanate. Further examples include aliphatic diamines such as ethylenediamine, butylenediamine, tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decalin, and bis(aminomethyl)tricyclodecane; and diamines having an aromatic ring such as bis(4-aminophenyl)ether, paraphenylenediamine, and bis(aminomethyl)naphthalene. Further examples include dithiols such as 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexaneedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, 1,14-tetradecanedithiol, 1,16-hexadecanedithiol, and 1,18-octadecanedithiol.Among these, ethylene glycol, ethylenediamine, butylenediamine, Ca, Mg, and Zn are preferred, and these may be used alone or in combination of two or more.

[0037] 1-4. Ester compounds (I) Ester compound (I) is an ester compound formed by the reaction of a carboxy group of compound (A') with a hydroxy group of compound (B') to form an ester bond, and is represented by (A')-(B'). Compound (I) can be synthesized by a known method. For example, it can be synthesized by a known method, such as a method in which composition (A) and composition (B) are heated (e.g., 150 to 300°C) in a solvent in the presence of an acid catalyst (e.g., Lewis acid) to react compound (A') and compound (B') to esterify them.

[0038] As another method for obtaining compound (I), compound (A') may be converted into a carboxylic acid derivative, and the carboxylic acid derivative of compound (A') may be reacted with compound (B'). Examples of the carboxylic acid derivative include metal salts and acyl groups. Specific examples of compound (I) include compounds of the following general formula (5). [ka] The descriptions of general formula (3) and general formula (4) are used for n2 and n4, respectively.

[0039] By introducing an ester moiety into the approximate center of compound (I), compatibility with resins can be improved, while maintaining sustained lubrication and preventing bleed-out. Furthermore, the combination of an ester moiety and two saturated hydrocarbon chains with 24 or more carbon atoms results in excellent compatibility with polar polymers. Furthermore, the presence of two saturated hydrocarbon chains with 24 or more carbon atoms can improve the solvent resistance of molded articles and coatings. Furthermore, the presence of two saturated hydrocarbon chains with 24 or more carbon atoms can enhance the bleed-out function required of an external lubricant. Furthermore, the presence of two saturated hydrocarbon chains with 24 or more carbon atoms significantly suppresses volatility and prevents odors. Because of its excellent heat resistance, it is useful as an external lubricant for molding resin compositions that require high-temperature processing (e.g., around 300°C).

[0040] 1-5. Compound (II) Compound (II) is represented by the formula: Compound (A')-Linking Group (C)-Compound (A'), obtained by reacting the carboxyl group of Compound (A') with Linking Group (C) in a molar ratio of 2:1. Linking Group (C) has two or more functional groups for bonding two molecules of Compound (A'). Compound (II) can be synthesized by a known method. For example, Compound (II) can be obtained by reacting the carboxyl group of Compound (A') with a compound having, for example, two hydroxyl groups as the above-mentioned Linking Group (C). Compound (II) can be obtained by adding an acid as a catalyst for esterification and heating the mixture. Another method for obtaining Compound (II) is to convert the carboxylic acid of Compound (A') into a carboxylic acid derivative and then reacting the carboxylic acid derivative of Compound (A') with Linking Group (C).

[0041] Furthermore, by reacting the carboxy group of compound (A') with, for example, a primary or secondary amine salt or a primary or secondary amine compound as the linking group (C), compound (II) having two amide bonds can be obtained.

[0042] Furthermore, a salt obtained from the carboxyl group of compound (A') and the linking group (C) of an alkali metal salt or alkaline earth metal salt is also suitable as compound (II). Compound (II) can also be said to be a carboxylate metal salt composition of a carboxylate anion and a metal cation.

[0043] Specific examples of compound (II) include any of the compounds represented by the following general formula (6). [ka] The description of general formula (3) is used for n2, provided that the two n2s in the formula may be the same or different. The description of general formula (1) is used for X.

[0044] By introducing an ester, amide, urethane, or the like into the approximate center of compound (II), the compatibility with resins can be improved, while maintaining sustained lubrication and preventing bleed-out. Furthermore, the presence of two saturated hydrocarbon chains with 24 or more carbon atoms enhances the compound's function as an external lubricant. Furthermore, because of its excellent heat resistance, it is useful as an external lubricant for molding resin compositions that require high-temperature processing (e.g., about 300°C).

[0045] 1-6.Mixture (III) Mixture (III) is a mixture for obtaining compound (I) and contains composition (A) and composition (B), each containing a precursor of compound (I). To efficiently obtain compound (I), the ratio of compound (A'):compound (B') is preferably 1.1:0.9 to 0.9:1.1, and more preferably 1.05:0.95 to 0.95:1.05. Mixing composition (A) and composition (B) can improve heat resistance compared to mixing them alone.

[0046] Mixture (III) is prepared by reacting compound (A') with compound (B') when heated during molding, for example, to obtain compound (I). Components of composition (A) and composition (B) may remain in the resin composition. Mixture (III) provides compound (I) during molding, etc., and therefore, compared to when composition (A) and composition (B) are used as release agents, volatility is reduced, improving continuous releasability and providing the same effect as a release agent using compound (I).

[0047] 2.Resin composition The resin composition of the present disclosure (hereinafter also referred to as the present resin composition) contains resin (G) and the present mold release agent. The content of the mold release agent in the present resin composition can be appropriately designed depending on the application. In the case of applications involving injection molding of engineering plastics, the content of the mold release agent is, for example, 0.001 to 30 parts by mass per 100 parts by mass of resin (G). From the viewpoints of improving productivity and facilitating release of a molded article from a mold, the content is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass.

[0048] Examples of molding methods for resin compositions include injection molding, compression injection molding, transfer molding, extrusion molding, blow molding, and coating. The molding temperature is usually about 150 to 300°C, and heat resistance is required so that the release agent remains without volatilizing during molding. The addition of the release agent to the resin composition significantly suppresses volatilization of the release agent, resulting in excellent heat resistance.

[0049] The type of resin (G) is not limited, but a thermoplastic resin is preferred. Suitable examples of resin (G) include polyamide resin, polyvinyl chloride, olefin resin such as polyethylene, vinyl acetate copolymer, polystyrene, ABS resin, polyester resin, polyacetal resin, polyurethane resin, epoxy resin, phenol resin, acrylic resin, polyamide resin, and polyimide resin. The resin may be a homopolymer or a copolymer. Polymer blends may also be used.

[0050] For example, polyamide resins tend to stick strongly to heated mechanical parts. Therefore, when a high concentration of filler is added, the flowability deteriorates during the injection molding process, leading not only to decomposition of the polyamide resin but also to deterioration of the quality of the molded product. The addition of the mold release agent of the present disclosure can alleviate these problems and provide excellent molded products.

[0051] The softening point of the resin (G) depends on the application, but is preferably 100 to 300°C from the viewpoint of the melting point of the release agent and heat resistance.

[0052] The resin composition may contain other additives within the scope of the present disclosure. For example, ultraviolet protection agents, antistatic agents, inorganic fillers such as thermally conductive fillers, antioxidants, flame retardants, antibacterial agents, antifungal agents, foaming agents, curable compounds, pigments, etc. may be added. Furthermore, within the scope of the present disclosure, release agents other than those defined as release agents in the present disclosure, internal lubricants, etc. may be added.

[0053] The resin composition can be suitably used as a composition for forming a molded body, and is suitable as a mold release agent when a resin composition such as a thermoplastic resin is molded in a mold.

[0054] The present resin composition is produced by mixing raw materials. For example, it can be produced using various kneaders. The present resin composition contains the present mold release agent, which significantly improves the releasability of the molded article after molding from the mold cavity.

[0055] In a resin composition primarily composed of mixture (III), compound (A') in composition (A) and compound (B') in composition (B) are esterified by heat during molding. Compared to the case of compound (I) alone, in a resin composition primarily composed of mixture (III), composition (A) and composition (B) have excellent compatibility with resin (G). Meanwhile, heating causes compound (A') and compound (B') to form an ester bond, converting all or part of mixture (III) into compound (I). This improves the heat resistance of the release agent, improves mold releasability, and provides excellent continuous mold releasability. Therefore, the release agent can have both external and internal lubricant properties. Furthermore, resin compositions using the release agent of the present disclosure exhibit excellent sharp melt properties, colorability, and chemical resistance.

[0056] 3. Molded body The molded article of the present disclosure is obtained by molding the resin composition of the present disclosure. Molding can be performed by known methods such as injection molding, vacuum molding, blow molding, extrusion molding, and calendar molding. The addition of the present mold release agent to the resin composition can effectively reduce frictional resistance with the mold surface, etc. As a result, for example, good fluidity can be maintained during injection molding. Furthermore, the molded article exhibits excellent mold release properties when released from the mold. [Example]

[0057] The present disclosure will be described in more detail below with reference to examples, but the scope of the present disclosure is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass".

[0058] a. Ingredients, abbreviations, product names, etc. The abbreviations and product names used in the examples are shown below. (Composition (A) etc.) Unicid 350: manufactured by NuCera, Mz / Mn = 1.68. Contains about 80 mass% of compound (A') having an average carbon number of 25 in the saturated hydrocarbon chain, 1 carboxy group, and Mz / Mn = 1.68, and about 20 mass% of polyethylene. Montan S: BASF, Mz / Mn = 1.97, average number of carbon atoms in saturated hydrocarbon chain = 24, number of carboxyl groups = 1 Octacosanoic acid: manufactured by Tokyo Chemical Industry Co., Ltd., Mz / Mn=1.03, average number of carbon atoms in the saturated hydrocarbon chain=28, number of carboxyl groups=1 (Composition (B)) Unilin 350: manufactured by NuCera, average number of carbon atoms in saturated hydrocarbon chain = 25, number of hydroxyl groups = 1, contains approximately 20 mass % polyethylene. Octacosanol: manufactured by Tokyo Chemical Industry Co., Ltd., average number of carbon atoms in the saturated hydrocarbon chain = 28, number of hydroxyl groups = 1 (others) Calcium hydroxide: manufactured by Tokyo Chemical Industry Co., Ltd. Magnesium hydroxide: manufactured by Tokyo Chemical Industry Co., Ltd. Zinc hydroxide: manufactured by Tokyo Chemical Industry Co., Ltd. Cobalt hydroxide: manufactured by Tokyo Chemical Industry Co., Ltd. Ethylene glycol: Tokyo Chemical Industry Co., Ltd. 1,4-Diaminobutane: Tokyo Chemical Industry Co., Ltd. (resin) P1: Duracon M90-44, Polyplastics Co., Ltd. P2: Nylon 1025SR: Unitika

[0059] b.Measurement method <Polydispersity Mz / Mn> Measurements were performed using a Tosoh GPC (gel permeation chromatography) "HLC-8420 GPC" column with three "TSKgel SuperHZM-N" (Tosoh GPC column: 4.6 mm ID x 15 mm size) columns connected in series. The eluent was THF at a flow rate of 0.3 mL / min, a pressure of 6.0 MPa, and a column temperature of 40°C. The sample was dissolved in the eluent to a sample concentration of 0.5% by mass. To avoid residual dissolution, 10 μL of the filtrate was filtered through a syringe filter (NP-42213-ACF; Tosoh) and injected. Peaks derived from the blank were excluded, and Mz and Mn were determined using polystyrene equivalent values ​​to calculate the polydispersity index.

[0060] c. Evaluation method <Heat resistance> Using a simultaneous thermogravimetry and differential thermal analysis (TG / DTA) instrument DTG-60A manufactured by Shimadzu Corporation, 10 mg of each release agent from each of the examples and comparative examples was heated from 40°C to 300°C at a rate of 10°C / min in an air atmosphere, and then maintained at 300°C for 30 minutes, and the mass loss rate was measured, and the heat resistance was evaluated according to the following criteria. +++: 20% or less ++: Over 20% and under 40% +: Over 40% and under 60% NG: Over 60%

[0061] <Liquidity> The fluidity of the release agents of each Example and Comparative Example was measured according to the method specified in JIS K 7210:1999 (ISO 1133:1997), and evaluated according to the following criteria: The improvement in MFR (250°C, 2.16 kg) when 0.2% by mass of the release agent was added to the polyacetal was evaluated, compared with the MFR (250°C, 2.16 kg) of the polyacetal alone. +++: Over 60% ++: Over 40% and under 60% +: Over 20% and under 40% NG: 20% or less

[0062] <Mold releasability> The mold release force of the resin compositions of each Example and Comparative Example was determined by the following method. The mold release force was evaluated by injection-molding a cylindrical molded object and defining the maximum ejection force when the molded object was released from the mold using a ring-shaped ejector. The percentage decrease in mold release force when 0.2% by mass of a mold release agent was added to polyamide 6 was compared to the mold release force of polyamide 6 alone and evaluated according to the following criteria. +++: Less than (1 / 20) ++: (1 / 20) or more, less than (1 / 10) +: (1 / 10) or more but less than (1 / 5), NG: (1 / 5) or more

[0063] <Continuous release> The continuous mold releasability of the resin compositions of each Example and Comparative Example was measured by the following method and evaluated according to the following criteria: 0.5% by mass of a mold release agent was added to polyamide 6 and injection-molded once, followed by continuous injection molding of polyamide 6 alone. The injection molding was stopped when polyamide 6 residues adhered to the mold, and the total number of moldings up to that point was recorded as the number of continuous mold releases. +++: 30 or more times ++: 20 or more times, less than 30 times +: 10 or more times, less than 20 times NG: Less than 10 times <Coloring chromaticity> The color chromaticity of the resin composition of each example and comparative example was measured by the following method and evaluated according to the following criteria: The release agent was placed in a heat-resistant container and heated at 175°C in an air atmosphere for 3 hours, then allowed to cool to room temperature, and the color difference ΔE before and after heating was measured. +++:ΔE≦5 ++:5<ΔE≦10 +:10<ΔE≦15 NG:15<ΔE

[0064] d. Synthesis of Compounds (I) and (II) <Synthesis Example 1> 226.48 g of UniCid-350 (acid value: 117.06 mg KOH / g) and 198.85 g of UniLin-350 (hydroxyl value: 126.98 mg KOH / g) were weighed into a 1 L separable flask and heated to 140°C under a nitrogen atmosphere to melt. 0.77 g of p-toluenesulfonic acid monohydrate was added as an esterification catalyst, and the reaction was carried out at 140°C for 7 hours under a nitrogen atmosphere while distilling off the by-product water using a Dean-Stark tube. After the reaction was completed, the contents were poured into a Teflon vat and allowed to cool to room temperature, yielding the compound of Synthesis Example 1 (pale yellow solid).

[0065] <Synthesis Example 2 and Comparative Synthesis Example 101> Synthesis was carried out in the same manner as in Synthesis Example 1, except that the raw materials shown in Table 1 were changed.

[0066] <Synthesis Example 3> 383.46 g of UniCid-350 (acid value: 117.06 mg KOH / g) was weighed into a 1 L separable flask and melted by heating at 140°C under a nitrogen atmosphere. 26.94 g of calcium hydroxide was added, and the reaction was carried out for 7 hours at 140°C under a nitrogen atmosphere while the by-product water was distilled out of the reaction system using a Dean-Stark tube. After the reaction was completed, the contents were poured into a Teflon tray and allowed to cool to room temperature, yielding the compound of Synthesis Example 3 as a beige solid. The NMR chart of the resulting compound is shown in Figure 1, and the IR spectrum is shown in Figure 2. 1 H-NMR (400 MHz, deuterated solvent: bromobenzene-d5, reference peak: deuterated solvent peak used as reference peak, measurement temperature 130 °C, δ (ppm): 2.440, 1.762, 1.245, 1.224, 0.830, 0.804, 0.785, 0.768) IR spectrum (measurement method: ATR, 2954.44 cm -1 , 2916.00cm -1 , 2848.70cm -1 , 1708.82cm -1 , 1547.62cm -1 , 1464.35cm -1 , 1377.37cm -1 , 1319.54cm -1, 1110.87cm -1 , 888.67cm -1 , 719.33cm -1 , 671.47cm -1 , 542.18cm -1 )

[0067] <Synthesis Examples 4 to 6, Comparative Synthesis Example 102> Synthesis was carried out in the same manner as in Synthesis Example 3, except that the raw materials shown in Table 1 were changed.

[0068] <Synthesis Example 7> 362.37 g of UniCid-350 (acid value: 117.06 mg KOH / g) was weighed into a 1 L separable flask and heated to 140°C under a nitrogen atmosphere to melt. 22.35 g of ethylene glycol and 0.68 g of p-toluenesulfonic acid monohydrate were added as an esterification catalyst, and the reaction was carried out at 140°C for 7 hours under a nitrogen atmosphere while distilling off the water by-produced outside the reaction system using a Dean-Stark tube. After the reaction was completed, the contents were poured into a Teflon tray and allowed to cool to room temperature, yielding the compound of Synthesis Example 7 (pale yellow solid).

[0069] <Comparative Synthesis Example 103> Synthesis was carried out in the same manner as in Synthesis Example 7, except that the raw materials shown in Table 1 were changed.

[0070] <Synthesis Example 8> 362.37 g of UniCid-350 (acid value: 117.06 mg KOH / g) was weighed into a 1 L separable flask and heated to 140 °C under a nitrogen atmosphere to melt. 31.73 g of 1,4-diaminobutane and 0.93 g of 2,4-bis(trifluoromethyl)phenylboronic acid as an amidation catalyst were added, and the reaction was carried out for 7 hours at 140 °C under a nitrogen atmosphere while distilling off the water by-product outside the reaction system using a Dean-Stark tube. After the reaction was completed, the contents were poured into a Teflon tray and allowed to cool to room temperature, yielding the compound of Synthesis Example 8 (pale yellow solid).

[0071] <Comparative Synthesis Example 104> Synthesis was carried out in the same manner as in Synthesis Example 8, except that the raw materials shown in Table 1 were changed.

[0072] [Table 1]

[0073] e. Evaluation of release agents (Examples 1 to 8, Comparative Examples 1 to 4) The products (including unreacted reactants) obtained in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 101 to 104 were used as release agents (see Table 2). The heat resistance and color intensity of each release agent were evaluated, and the results are shown in Table 2. [Table 2]

[0074] f. Evaluation of resin composition [Example 11] A resin composition of Example 11 was obtained by kneading 100 parts of P1 as a resin and 0.2 parts of the release agent of Synthesis Example 1 as a release agent at 200°C using a Labo Plastomill.

[0075] [Examples 12 to 23, 31 to 43, 51 to 63, Comparative Examples 11 to 15, 31 to 35, 51 to 55] Resin compositions of Examples 12 to 23, 31 to 43, 51 to 63 and Comparative Examples 11 to 15, 31 to 35, and 51 to 55 were obtained in the same manner as in Example 11, except that the type and amount of resin and the type and amount of release agent were changed as shown in Tables 3 to 5. However, when resin (G) was P2, the kneading temperature was 240°C.

[0076] Tables 3 to 5 show the evaluation results of the flowability, releasability, and continuous releasability of the resin compositions of each example. [Table 3] [Table 4]

[0077] [Table 5]

[0078] It was confirmed that the release agents prepared using Comparative Synthesis Examples 101 to 104, which use long-chain carboxylic acids with an Mz / Mn ratio exceeding 1.97, have problems with heat resistance and / or color chromaticity, as shown in Comparative Examples 1 to 4. On the other hand, it was confirmed that the release agents of the present disclosure are excellent in heat resistance and color chromaticity, as shown in Examples 1 to 8. Furthermore, it was confirmed that the resin compositions using release agents made of long-chain carboxylic acids with an Mz / Mn ratio exceeding 1.97 are inferior in terms of releasability and the like to the resin compositions using the release agents of the present disclosure, as shown in Comparative Examples 11 to 15, 31 to 35, and 51 to 55. [Industrial Applicability]

[0079] The release agent of the present disclosure is suitably used as a lubricant, nucleating agent, release agent, or dispersing aid during plastic molding.

Claims

1. an ester compound (I) represented by (A')-(B') (hereinafter referred to as compound (I)) obtained by reacting a carboxy group of a composition (A) (hereinafter referred to as composition (A)), which contains 0 to 25 mass% of polyethylene and 75 to 100 mass% of a saturated hydrocarbon-based compound having a saturated hydrocarbon chain with an average carbon number of 24 or more, one carboxy group, and a polydispersity index Mz / Mn of 1.8 or less (hereinafter referred to as compound (A')), with a hydroxy group of a composition (B) (hereinafter referred to as composition (B)), which contains 0 to 25 mass% of polyethylene and 75 to 100 mass% of a saturated hydrocarbon-based compound having a saturated hydrocarbon chain with an average carbon number of 24 or more and one hydroxy group (hereinafter referred to as compound (B')); Compound (II) represented by (A')-(C)-(A') obtained by reacting the carboxy group of compound (A') with the reactive functional group of linking group (C), and a mixture (III) for obtaining compound (I), the mixture containing composition (A) containing a precursor of compound (I) and composition (B); A release agent comprising at least one selected from the group consisting of:

2. 2. The release agent according to claim 1, wherein the linking group (C) is represented by general formula (1). 【Chemical 1】 (wherein X represents a divalent group selected from the group consisting of an optionally substituted linear or branched hydrocarbon group, an optionally substituted alicyclic hydrocarbon group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, a metal atom, and a group represented by general formula (2), or a divalent group formed by combining two or more of the same or different groups selected from the above group; Y １ , Y ２ represent, independently of each other, a hydroxy group, a thiol group, an amino group, or an isocyanate group. 【Chemistry 2】 (However, Z １ , Z ２ are each independently —O—, —S—, or —SO ２ -, -Si(Me) ２ -, -N=N-, -NH-, and -NR ４ - is a divalent group selected from the group consisting of R １ ~R ３ each independently represents a linear or branched hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or —C(CF ３ ) ２ -, or a divalent group formed by combining two or more of the same or different groups selected from the above group, R ４ is a linear or branched hydrocarbon group having 1 to 12 carbon atoms, and n is an integer of 0 or more.

3. 3. The mold release agent of claim 2, wherein said metal atom of said X is selected from the group consisting of Ca, Mg, and Zn.

4. The mold release agent according to claim 1, which comprises the compound (I) or (II) and further comprises a composition (A).

5. The release agent according to claim 1, further comprising a polyethylene component.

6. The dipole moments S of the compounds (I) and (II) calculated by quantum chemical calculation are 1.7≦S≦4.7 Debye, 2. The mold release agent according to claim 1, wherein in the case of the mixture (III), the dipole moment S of the compound (I) obtained from the mixture (III) is 1.7≦S≦4.7 Debye.

7. A resin (G) and the release agent according to any one of claims 1 to 6, The resin composition contains the release agent in an amount of 0.01 to 20 parts by mass per 100 parts by mass of resin (G).

8. A molded article formed from the resin composition according to claim 7.

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